2-methylene indoline azomethine groupcontaining basic dyestuffs



United States Patent O This application is a continuation of my application Ser. No. 144,572, filed Oct. 12, 1961, and now abandoned, which in turn is a continuation of my application Ser. No. 754,525, filed Aug. 12, 1958, and now abandoned.

The present invention relates to new basic dyestuffs; more particularly it relates to basic dyestuffs of the formula In this formula R stands for lower alkyl, R means lower alkyl, A stands for one of the radicals O C H C H3 03 (lo g \N/ and X means an acid radical used for salt formation in basic dyestuffs.

The new dyestuffs (I) are preferably produced by reacting the basic starting dyestuffs of the formula i if I wherein A and R have the above mentioned significance, -in the presence or absence of a solvent or diluent, with a suitable quaternizing alkylation agent and at elevated temperature, if desired, under pressure. After completion of the reaction the quaternary products precipitate in most cases in a crystalline form. 1

The dyestuff bases used for quaternizing and corresponding to the formula wherein A and R have the above mentioned significance,

are easily obtainable by treating with alkalies the corresponding basic dyestuffs isolated as salts and correspondf it l wherein A, R and X have the above mentioned significance.

The basic starting dyestuffs are obtainable from the 1,3,3-tri-lower alkyl-2-methylene-indoline compounds and the appropriate amine components in known manner.

The lower alkyl groups in the above identified compounds are preferably those containing 1 to 4 carbon atoms, such as CH -C H and C H The amino compounds to be used for the preparation of dyestuffs (I) are 1-amino-4-methoxybenzene, l-amino- 2 methoxybenzene, 1 amino-2,4- or -2,5-dimethoxybenzene, 1-amino-4-acetylaminobenzene, 1amino-4-phenylazobenzene, 1- or Z-aminonaphthalene and dehydrothiotoluidine.

As quaternizing agents there may be used inter alia dimethyl sulfate and diethyl sulfate or methyl iodide and toluene sulfonic acid esters.

Suitable solvents or diluents are for example acetone, ligroin, benzine, benzene, toluene and xylene.

The invention further relates to new basic dyestufls of the formula 'In this formula R stands for lower alkyl, R means lower alkyl, R stands for .ca-rbo lower 'alkoxy, lower alkoxy, chloro, cyano or nitro, A stands for one of the radicals and X means an acid radical used for salt formation in basic dyestuffs.

The new dyestuffs (II) are preferably produced by reacting the basic starting dyestuffs of the formula Patented Oct. 3, 1967 wherein A R and R have the above mentioned significance, in the presence or absence of a solvent or diluent, with a suitable quaternizing agent and at elevated temperature, if desired, under pressure. After completion of the reaction the quaternary products precipitate in most cases in a crystalline form.

The dyestuff bases used for quaternizing and corresponding to the formula wherein A R and R have the above mentioned significance, are easily obtainable by treating with alkalies the corresponding basic dyestuffs isolated as salts and corresponding to the formula wherein A R R and X have the above mentioned significance.

As heterocyclic compounds which are to introduce into the dyestuffs (II) the part idine and 1-amino-4-methylbenzene.

As quaternizing agents there may be used inter alia dimethyl sulfate, diethyl sulfate, methyl iodide, and toluene-sulfonic acid esters.

Suitable solvents or diluents are for example acetone, ligroin, benzine, benzene, toluene and xylene.

The new dyestufis (I) and (II) are suitable for the dyeing of textiles, paper, coir, leather and other materials. The compounds are free from sulfonic acid and carboxylic acid groups and therefore especially suitable for the dyeing of articles from polyacrylonitrile, clear shades of very good fastness properties, especially excellent fastness to light being thus obtained.

In the following examples the parts by Weight and the parts by volume being in the ratio of grams to millilitres.

Example 1 The hydrazo dyestulf from diazotized 1-amino-4-methoxy-benzene and 1,3,3-trimethyl-2-methylene-indoline is converted into the azo form by treating it with a sodium carbonate solution in an aqueous suspension. After recrystallization from methanol the compound melts at 152154 C. 30.7 parts by Weight of this compound are dissolved with heating in 100 parts by volume of toluene and treated dropwise with 12.6 parts by weight of dimethyl sulfate. The reaction mixture is then heated on a boiling water bath, the quaternary dyestutf separating out as yellow crystals already after a short time. The mixture is heated on the boiling water bath for another 3 hours, cooled and the dyestuff is filtered off with suction. The methyl sulfate of the dyestulf is thus obtained in the pure state; a further purification is unnecessary.

The dyestuff draws on polyacrylonitrile fibres in a clear yellowish orange shade and is especially distinguished by an outstanding fastness to light. Acetate rayon is also dyed in a clear yellowish orange shade.

When using the starting components listed in the following table for the manufacture of the basic hydrazo and azo dyestuffs and alkylating the azo dyestufifs with dimethyl sulfate according to the method described above, quaternary dyestutfs are obtained which dye fibres from polyacrylonitrile and acetate rayon in the indicated shades.

Dlazo component Coupling component Shade 1aminonaphthalene 1,3,3-tr im ethyl-methylene Yellowlsh indoline. orange. 4-aminoazobenzene -.do Do. 1-amino-2-methoxybenzene. .-do Greenish yellow. l-amino-2,4-dimethoxyd0 Yellow ish benzene. orange. 1-amino-2,5-d1methoxy- -do Orange.

benzene. l-arninot-aeetylamlno- 1,3,B-trlmethyl-Z-methylene- Do.

benzene. indoline. Dehydrothiotoluidine .do Do. 2-arm'nonaphthalene do Yellowish Orange. l-aminoA-methoxybenzene. 1,3,3-trlmethyl-5-methoxy- Do.

Z-methylene-iodoline. 1-amlno-2,4-dimethoxy- 1,3,3-trimethyl-5-el11oro-2- Do.

benzene. methylene-indoline. laminot methoxybenzene. .do. Orange. 1-amlno-4-methylbenzene 1,3,3trimethyl-5-earbo- Yellowish methoxy-2-methyleneorange. indoline. 1-amln0-4-methoxyb enzene- .do... Orange. Aminoazotoluene .do o. l-amlno-tt-rnethylbenzene. 1,3,3-tr1methy tr Yellowish methylene-indoline. orange.

Example 2 The hydroazo dyestulf from diazotized 1-amino-4-methoxybenzene and 1,3,3-trimethyl-2-methylene-indoline is converted into the azo form by the method described in Example 1 (MP. 152-154 C.). 15.4 parts by weight of this compound are dissolved in 50 parts by volume of toluene and treated with 9.3 parts by weight of 4-toluene sulfonic acid methyl ester. The reaction mixture is then heated on a boiling water bath, a yellowish orange crystalline precipitate being formed after some time. The mixture is heated for a total of 5 hours, then cooled and the dyestuff in the form of the 4-toluene sulfonate is filtered 01f with suction.

In a similar manner to that there is obtained by reacting with methyl iodide the iodide of the quaternary dyestuff which can be recrystallized from alcohol.

The dyestuffs dye fibres from polyacrylonitrile and acetate rayon in yellowish orange shades.

Example 3 15.4 parts by weight of the starting dyestutf used in Example 2 are dissolved with heating in 40 parts by volume of toluene and treated dropwise with 7.7 parts by weight of diethyl sulfate. The mixture is then heated on a boiling water bath for 5 hours, whereby an oil separates. Upon cooling, the oily dyestufi solidifies'to form yellowish orange crystals which are isolated in usual manner. The dyestuff dyes acetate rayon and polyacronitrile fibres in a yellowish orange shade.

When using instead of diethyl sulfate the equimolecular amount of 4-toluene sulfonic acid ethyl ester, heating to C. for 6 hours and working up in an analogous manner, a dyestuff of similarly good fastness properties is obtained. When using instead of 4-toluene sulfonic acid ethyl ester an excess of ethyl iodide and proceeding according to the same method a dyestuff is obtained which dyes polyacrylonitrile fibres also in a yellowish orange shade of outstanding fastness.

Example 4 The hydrazo dyestuif from diazotized 1-amino-4-methoxy-benzene and 1,3,3-trimethyl-2-methylene-indoline is converted into the corresponding azo compound according to the method described in Example 1. 15.4 parts by weight of this compound are dissolved with heating in 50 parts by volume of toluene and treated with 8.3 parts by weight of butyl bromide. The mixture is then slowly heated to the boil and stirred under reflux on an oil bath at a bath temperature of 120-124 C. for 24 hours. After cooling the separated dyestuif is filtered oil? with suction. By dissolving in boiling water and salting out with common salt, the product is separated from the unreacted starting material. The dyestuif dyes fibres from polyacrylonitrile in a yellowish orange shade of outstanding fastness properties.

Example 5 61.2 parts by weight of the starting dyestutr' used in Example 4 are dissolved at 70 C. in 100 parts by volume of chlorobenzene and 27.7 parts by weight of dimethyl sulfate are added dropwise within 5 minutes. The mixture is then heated on a boiling water bath for 3 hours and the chlorobenzene is then blown off with steam. After the addition of some active carbon, steam is again introduced for a short period, the product is. filtered hot. and salted out with 100 parts by weight of common salt after the addition of 2 parts by 'volume of concentrated hydrochloric acid. The product is stirred overnight, filtered off with suction and washed with 100 parts by volume of a percent common salt solution. The dyestufr thus obtained is identical with the dyestuif described in Example 1.

Polyacronitrile fibres are introduced at 40 C. into an aqueous bath containing per litre 0.75 gram of glacial acetic acid, 0.4 gram of sodium acetate and 0.2 gram of the dyestuff obtained according to Example 1 (first dyestufl) using a liquor-to-goods ratio of 40:1. The bath is heated to the boil within to minutes and kept at this temperature for 30 to 60 minutes. The polyacrylonitrile fibres are then rinsed and dried. A yellowish orange dyeing is thus obtained of excellent fastness to wetting and light.

Example 6 A copying black is obtainable by mixing the following basic dyestuffs parts by weight of malachite green 15 parts by weight of methyl violet 15 parts by weight of fuchsine and 20 parts by Weight of the first dyestuff obtained according to Example 1.

wherein R stands for lower alkyl, R stands for lower alkyl, A stands for one of the radicals 60H: OCH3 OCH;

l O CH;

and X stands for an acid radical used for salt formation in basic dyestufis.

2. A basic dyestufi of the formula wherein R stands for lower alkyl, R stands for lower alkyl, R stands for carbo lower alkoxy, lower alkoxy, chloro, cyano or nitro, A stands for one of the radicals OCH;

I .NHOCCH s on,

and X stands for an acid radical used for salt formation in basic dyestufis.

3. The basic dyestufl of claim 2 wherein R stands for ""NO2.

4. The basic dyestuff of the formula CH3 C:CH:

\ CCH=NN N/ CH 6 CH3 CH3 -5. The basic dyestufl of the formula C a CCH3 bcH=N- -N--0cm o1- I? CH: 6 CH3 CH3 7 6. The basic dyestufl of the formula 3. 1 o-cEa C 8 CH, E

I CH3 CH3 8. The basic dyestuif of the formula 10. The basic dyestulf of the formula CCH5 '11; The basic dyestufi of the formula /CH3 7' i -o -oHa 8 12. The basic dyestulf of the formula /CHa -CCH I CH3 CH3 13. The basic dyestuff of the formula N02 CH CCH3 c-cH=N- -N@0Ea CH3 7 14. The basic dyestufi of the formula NO: /OH3 -(IJCHa 0-c11=N-1 I-ocm I OH; CHa

15. The basic dyestuif of the formula I COH=N--NOCHs W CH: (3H3 OTHER REFERENCES Rosenhauer et al., Ber. Deut. Chem, vol. 59, pp.

CHARLES B. PARKER, Primary Examiner.

FLOYD D. HIGEL, Assistant Examiner. 

1. A BASIC DYESTUFF OF THE FORMULA 